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Reis'aued Nov. 24, 1953 UNITED FUNGICIDAL SALTS OF ALKYL'ENEBISDITHIOCARBAMIC ACID William F. Hester, deceased, late of Drexel Hill,

Pa., by Rohm Philadelphia, Fa., of Delaware No Drawing. Original No. 27,1943, Serial No. 40'! 8:. Haas Company,

a corporation of the asslgnee, State 2,317,765, dated April 674, August20, 1941.

Application for reissue October 24, 1952, Serial 3 Claims.

Matter enclosed in heavy brackets 1 appears in the original patent butforms no part of this reissue specification; matter printed in italicsindicates the additions made by reissue.

This invention relates to fungicidal composi tions suitable forapplication to living plants. More particularly it relates to fungicidalcompositions containing as an active agent a compound of the formulawherein R represents a divalent hydrocarbon group or a divalentaliphatic" chain containing more than three carbon atoms separated by atleast one nitrogen atom to form alkylene groups of at least two carbonatoms each, R and R" taken individually represent hydrogen jointlyrepresent a divalent hydrocarbon group which in conjunction with theN-RN group forms a heterocycle, and M represents a salt-forming group ormetal.

While sulfur and some of the sulfur-containing compounds are known tohave fungicidal value, not all compounds containing sulfur arefungicidal. Nor are all sulfur compounds safe to use on living plants.

I have found that the sulfur-containing compounds of the above formulaare exceptionally effective in fungicidal compositions and are low inphytocidal action. Thus compositions containing a compound of theformula MSCN-RNCSM l I fill g are useful for preventing and controllingfungus growth on living plants and are suprisingly more effective thanpreviously known compounds which contain a single dithiocarbamate groupor a thiuram grouping.

These compounds are prepared by reacting a polyamine and carbondisulfide, generally in the presence of a free base. In preparing themthere may be used a dior other poly-amine having hydrogen atomsavailable on nitrogen atoms in the amine groups. Suitable polyaminesinclude ethylenediamine, propylenediamine, tetramethylenediamine,piperazine, paraphenylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, bis(aminoethyl)propylenediamine, etc. When one of these amines is reacted with carbondisulfide, there results the amine salt of a bisdithiocarbamic acid. Ifthe reaction between amine and carbon disulfide is carried out in thepresence of a strong base, the

amine salt group is displaced and a salt formed from the cation of thebase.

AS .3 1 8-58 there or taken may be used lithium, sodium, potassium,calcium, barium, etc. hydroxide or a strongly basic quaternary ammoniumhydroxide, such as benzyl trimethyl ammonium hydroxide or dibenzyldiethyl ammonium hydroxide. A soluble salt of a bisdithiocarbamic acidmay be converted to an insoluble or less soluble salt by metathesis.

The salt, whether soluble or insoluble, may be suspended or dissolved inan aqueous spray or may be mixed with or coated on a carrier, such asclay, magnesium carbonate, or similar inert material, and applied from adust or from an aqueous spray. The salt may be used" as the solefungicidal material or it may be used in conjunction with otherfungicidal agents. Also, the salt of a bisdithiocarbamic acid may beused in conjunction with an insecticidal agent or insecticidal agents.

- Example 1 A mixture of 250 parts of 72% ethylenediamine and 480 artsof a 50% aqueous sodium hydroxide solution was stirred and externallycooled while 478 parts of carbon disulflde was added dropwise below thesurface of themixture. The addition of carbon disulfide required twohours. during which time the temperature was held below 25 C. Thereaction mixture was further stirred for two hours at the end of whichtime it set to a solid. This was recrystallized from 1800 parts ofanhydrous ethanol to give 868 parts of an air-dried solid which meltedwithin the range of 85-l10 C. and which consisted essentially of theclisodium salt of ethylene blsdithiocarbamic acid.

Tested againstspores or Macrosporium sarcinaeforme Cav. the aboveproduct had a Bordeaux coefiicient of 11 to 12 which is about threefoldthe coefificient of the dithiocarbamates which have heretofore beenproposed for insecticidal or fungicidal uses and which is many times thecoefficient for insoluble copper compounds which have been successfullyused.

Applied in aqueous sprays to living plants, the compound as preparedabove was highly effective in controlling black spot on rosebushes andscab on apple trees.

Example 2 A mixture of 302 parts of 73.5% propylenediamine and 320 partsof a 50% aqueous sodium hydroxide solution was stirred and external ycooled while 501 parts of carbon disulflde was added during a 45-minuteperiod. The reaction was stirred for about two hours when it set to asolid mass, which was recrystallized trom 700 3 parts of anhydrousethanol. There was obtained 700 parts of a solid, melting between 55 C.and 60 C. The product was finely powdered and applied from aqueoussprays to plants without evi dence of phytocidal action. At one poundper Uhundred gallons of spray excellent control of black spot on roseswas obtained.

Example 3 The sodium salt of ethylene bisdithiocarbamic acid wasprepared as in Example 1 and 2200 parts.

of the crystallized product dissolved in 10,000 parts of water. Asolution containing 2200 parts of crystalline copper sulfate, dissolvedin 10,000 parts of water, was mixed therewith, resulting inprecipitation of a copper salt. Theprecipitate was filtered, washed, anddried. The product amounted to 2278 parts and corresponded by analysisto (SSCHNC2H4NHCSS- Cu. It was finely ground and used in suspension inaqueous sprays which were applied to living plants with complete controlof fungus thereon.

dithiocarbamic acid] [5. A fungicidal composition having as an, activeingredient the ferric salt of ethylene bis- In an entirely comparablemanner there may I be prepared other insoluble or relatively insolublesalts of the bisdithiocarbarnic acids, such as the ferrous or ferricsalts, the zinc salt or the cadmium salt. All of these salts have beentested and found eiiective fungicidally. In one series of tests thesesalts were applied to roses in a garden where powdery mildew waspresent. The sprays were prepared with two poundsof a given salt perhundred gallons of spray. In some tests wetting and spreading agentswere used. After three applications the incidence of disease wasobserved and rated on a scale from ten to zero, the lower numbers beingbest. were rated at 3.3 and sections sprayed with flotation sulfur werealso rated at 3.3. The section sprayed with the above copperbisdlthiocarbamate were rated at 0.5; that with the ferrous salt at 1.0;that with ferric salt with a wetting agent prepared by reactingpolyglycerol, cocoanut fatty acid, and phthalic anhydride at 0.9; andthat with ferrous salt, with or without wetting agents, 2.3.

Pea seeds were dusted in a tumbler with 0.25% of their weight ofpowdered compounds and planted three-quarters of an inch deep. The percent. emergence was noted at the end of the first week and after thesecond, third, and fourth weeks. With the sodium salt of ethylenebisdithiocarbamate the per cent. emergence was found at these times tobe 18, 32, 45, and 63; with the cadmium salt 43, 50, 56, and 64. Withuntreated seed emergence was 1, 3, 8, and 20 while seed treated with astandard mercurypreparation for preventing damping-oil gave emergencefigures of 5, 7, 12, and 23.

I claim:

[1. A fungicidal composition having as an active ingredient a salt of analkylene bisdithiocarbamic acid] [2. A fungicidal composition having asan active. ingredient a salt of ethylene bisdithiocarbamic acid] [3. Afungicidal composition having as an active ingredient the disodium saltof ethylene bisdithiocarbamic acid] The unsprayed sections 4 [4. Afungicidal composition having as an active ingredient the cupric salt ofethylene bisdithiocarbamic acid] 6. The process of controlling fungusgrowth on living plants which comprises applying to the plant afungicidal composition having as an active ingredient a salt of analkylene bisdithlocarbamic acid.

7. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient a salt of ethylene bisdithiocar-.

' bamic acid.

8. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient a bivalent metal salt of ethylene bisdithiocdrbamicacid.

9. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient the sodium salt of ethylene bisdithiocarbamio acid.

10. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient the cupric salt of ethylene bisdithiocarbamic acid.

11. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient the ferric salt of ethylene bisdithiocarbamic acid.

12. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient the zinc salt of ethylene bisdithiocarbamic acid.

13. The process of controlling fungus growth on living plants whichcomprises applying to the plant a fungicidal composition having as anactive ingredient the cadmium salt of ethylene bisdithiocarbamic acid.

ROHM & HAAS COMPANY, Assignee of William F. Hester, deceased,

By STANTON C. KELTON,

Secretary.

References Cited in the file of this patent or the original patent UNITED. STATES PATENTS OTHER REFERENCES Levi et al.. Gazzetta ChimicaItaliana, vol. 59,

pages 681 to 686 (1929).

A. Ya. Yakubovich et al., Chemical Abstracts, vol. 34, page 3685.

